EP1497885B1 - Brennstoffzelle mit oxidoreduktase-enzymen im kathoderaum oder ggf. anodenraum - Google Patents

Brennstoffzelle mit oxidoreduktase-enzymen im kathoderaum oder ggf. anodenraum Download PDF

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Publication number
EP1497885B1
EP1497885B1 EP03717375A EP03717375A EP1497885B1 EP 1497885 B1 EP1497885 B1 EP 1497885B1 EP 03717375 A EP03717375 A EP 03717375A EP 03717375 A EP03717375 A EP 03717375A EP 1497885 B1 EP1497885 B1 EP 1497885B1
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EP
European Patent Office
Prior art keywords
enzyme
fuel cell
compartment
cathode
cell according
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EP03717375A
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English (en)
French (fr)
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EP1497885A2 (de
Inventor
Damien Feron
Alain Bergel
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Centre National de la Recherche Scientifique CNRS
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Centre National de la Recherche Scientifique CNRS
Commissariat a lEnergie Atomique CEA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a proton exchange membrane fuel cell, using at the level of the cathode compartments and optionally anodic oxidoreductase type enzymes.
  • the general field of the invention is therefore that of proton exchange membrane fuel cells.
  • a gas diffusion stack means, in the foregoing and the following, a battery for which the oxidant and the fuel feed their respective compartments directly in the form of a gas flow.
  • This mediator is 2-2'-azinobis (3-ethylbenzothiazoline-6-sulfonate).
  • this mediator is not only expensive but also degrades prematurely due to the production of free radicals, during the transfer of electrons between the cathode and the active site of the enzyme, via said mediator.
  • the electrons and protons produced are successively transferred to glucose oxidase associated with the FAD coenzyme to give a reduced system of the Gox-FADH 2 type , then the mediator to give MBH 2 , which finally transfers the electrons to the external circuit, in the direction of the cathode compartment.
  • the authors have grafted onto the surface of the cathode in contact with cumene peroxide a monolayer consisting of a microperoxidase intended to ensure the reduction of cumene peroxide.
  • the object of the present invention is therefore to propose a fuel cell which does not have the abovementioned disadvantages.
  • an oxidoreductase is understood to mean an enzyme capable of catalyzing an oxidation reaction of a first substrate (referred to as a suitable substrate within the scope of the invention) and a reduction reaction of a second substrate (consisting of oxygen within the scope of this invention).
  • the oxidoreductase type enzymatic catalyst incorporated in the cathode compartment catalyzes the oxidation reaction of a suitable substrate and the oxygen reduction reaction to hydrogen peroxide, said hydrogen peroxide being able to accept directly the electrons from the cathode without the need to resort, for example, to any electrochemical mediator.
  • the oxidoreductase type enzyme catalyst of the invention participates in the reaction of production of hydrogen peroxide (corresponding in the context of the invention to the oxidant of the cathodic reaction), this hydrogen peroxide directly participating in the cathodic reaction by accepting the electrons from the cathode to reduce to water.
  • the specific enzymatic catalyst of the invention is no longer involved in the mechanism for accepting the electrons of the cathode, this greatly simplifies the design of said cathode compared with previous embodiments.
  • the enzymatic catalysts according to the invention promote catalysis of the oxygen reduction in oxygenated water and the oxidation of a suitable substrate at ambient temperature, which facilitates the starting of the fuel cell.
  • the catalysis of the above-mentioned reactions, generated by the enzymatic catalysts according to the invention decreases from a certain temperature threshold.
  • a temperature must not be exceeded, it is possible to choose an appropriate oxidoreductase enzyme capable of reacting in a more limited manner at a given temperature.
  • the implementation of the present invention can thus make it possible to have an intrinsic safety of the cell, by resorting to a given enzyme.
  • the enzymatic catalysis according to the invention is also perfectly adjustable. Indeed, the aforementioned reactions will only be catalyzed if, in the cathode compartment, the appropriate substrate and oxygen are added, the suitable substrate corresponding to glucose, when the oxidoreductase corresponds to glucose oxidase. It is then possible to adjust this addition according to the needs of the user of the stack.
  • the fact of using enzymes, which do not intervene in the acceptance of the electrons coming from the cathode, can make it possible to replace the electrodes conventionally used in previous embodiments (such as graphite or noble metal electrodes, such as platinum and gold) by electrodes made of industrial materials or alloys such as stainless steels, aluminum alloys, nickel alloys or titanium or conducting polymer materials.
  • the cathode of the invention is made of stainless steel.
  • the enzymatic catalysts according to the invention have the advantage of being inexpensive and not to degrade prematurely.
  • the enzymes according to the invention capable of reducing dioxygen are oxidoreductases, which, according to the nomenclature in force, are identified by an EC number of EC type 1.X.3.Y, with 1 denoting the class of oxidoreductases, X characterizing the electron donor substrate, 3 denoting oxygen as the electron accepting substrate, Y specifically denoting an enzyme, which falls within the subclass defined by the three preceding numbers. It is understood that, according to the invention, these enzymes will catalyze the reduction of oxygen to hydrogen peroxide.
  • oxidoreductase type enzymes that are furthermore capable, by reaction with said suitable substrate, of generating acidification of the cathode compartment. , this acidification facilitating the reduction of oxygen to hydrogen peroxide and then the reduction of hydrogen peroxide in water on the surface of the cathode.
  • This phenomenon is particularly advantageous in the case where the cathode is made of stainless steel, insofar as the acidification of the cathode compartment can make it possible to activate the surface of the cathode, in order to facilitate the reduction of hydrogen peroxide in water. .
  • the oxidoreductase type enzymes may be selected from the group consisting of galactose oxidase, glucose oxidase, pyruvate oxidase, glutamate oxidase, alcohol oxidases.
  • galactose oxidase glucose oxidase
  • pyruvate oxidase glutamate oxidase
  • alcohol oxidases it is understood that the appropriate substrates are respectively galactose for galactose oxidase, glucose for glucose oxidase, pyruvate for pyruvate oxidase, glutamate for glutamate oxidase, an alcohol for alcohol oxidases.
  • the EC numbers of these enzymes are EC 1.1.3.4 for glucose oxidase, EC 1.1.3.9 for galactose oxidase, EC 1.2.3.3 for pyruvate oxidase, EC 1.4.3.7 for glutamate oxidase, respectively.
  • the oxidoreductase type enzyme used in the cathode compartment is glucose oxidase.
  • the active site thereof causes oxidation of the glucose substrate to glucono-1,4-lactone which is subsequently hydrolyzed to gluconic acid.
  • the same active site generates the reduction of oxygen to hydrogen peroxide which is then reduced to water by the electrons arriving from the cathode, the acidification of the cathodic compartment by gluconic acid favoring these two successive reductions.
  • Glucose oxidase also has the advantage of making it possible to constitute an intrinsic safety of the cell, insofar as the glucose oxidase is no longer active at around 70 ° C. It is therefore particularly advantageous for applications using a battery, according to the present invention, where this temperature must not be exceeded.
  • the catalysis of the anodic reaction i.e. the oxidation reaction of a fuel
  • the catalysis of the anodic reaction can be carried out by any type of catalyst, including metal catalysts.
  • the catalyst of the anode compartment is, according to the invention, an enzyme capable of catalyzing the oxidation of a suitable substrate, said substrate providing the fuel function.
  • the enzyme of the anode compartment is further able, by reaction with said substrate, to ensure an acidification of the anode compartment.
  • the enzyme of the anode compartment may be selected from the group consisting of hygrogenases, glucose oxidase, galactose oxidase, alcohol oxidases. It is understood that the substrates for the list of enzymes mentioned are respectively hydrogen, glucose, galactose, the appropriate alcohols.
  • the enzyme of the anode compartment is glucose oxidase and the fuel glucose.
  • the enzyme of the anode compartment according to the invention is directly involved in the anodic reaction, ie in the transfer of electrons from the fuel to the anode, this enzyme is advantageously immobilized at the same time. surface of the anode.
  • the immobilization of the enzyme can be carried out by standard methods known to those skilled in the art such as a simple adsorption, a co-crosslinking reaction with glutaraldehyde, the inclusion in the membranes of Nafion type polymer or in layers of surfactants deposited on the anode, electrostatic interactions with polyions adsorbed on the surface of the anode, grafting by covalent bonding.
  • the present invention can be applied to both gaseous diffusion batteries and batteries operating in an aqueous medium.
  • the enzyme (s) of the anode and / or cathode compartment and the substrate (s) may be introduced continuously or discontinuously into the respective compartments during operation of the cell.
  • the enzymes can be introduced as aerosols with the appropriate substrates.
  • the enzyme or enzymes of the anode compartment and / or cathode are adsorbed on the anode and / or on the cathode.
  • the enzyme or enzymes are, according to a particular embodiment, introduced directly. in the aqueous medium of the anode and / or cathode compartments, during assembly of the battery.
  • FIG. 1 represents the diagram of a battery according to the invention operating in an aqueous medium.
  • FIG. 2 represents the diagram of a stack, according to the invention, with gaseous diffusion, with catalysis of the cathodic reaction by glucose oxidase.
  • the stack used is a battery operating in an aqueous medium and is shown in FIG.
  • This battery has respectively a cathode compartment 1 and anode compartment 2 separated by a proton exchange membrane 4.
  • the electrodes are respectively a platinum grid for the anode 6 and a stainless steel plate for the cathode 8.
  • the saturation of the flow of water with dihydrogen or dioxygen is effected by bubbling of its respective gases in the water of the tanks 11, said gases being conveyed at the level of the tanks 11 by a dioxygen inlet 14 on the cathodic and by an arrival of dihydrogen 12 on the anodic side.
  • glucose and glucose oxidase are introduced at the reservoir 11 on the cathode side through an inlet 16 positioned near the oxygen inlet 14.
  • outlets 18 are provided to ensure the renewal of the aqueous medium.
  • the power provided is 70 to 280 times greater in the presence of glucose oxidase than without, for different values of electrical resistance as shown in Table 1 below.
  • the stack used is similar to the stack of Figure 1 described above.
  • the stack implemented according to this example, is represented in FIG.
  • This cell has respectively an anode compartment 20 and a cathode compartment 22 separated by a proton exchange membrane 24, the anode and the cathode being made of graphite.
  • platinum (1mg / cm 2 ) is used.
  • the anode compartment 20 has an inlet of hydrogen 26 which passes before its introduction into the compartment a device humidifier 28, while the cathode compartment has an oxygen inlet 30 passing through a humidifier device 28 and laterally an inflow of glucose and glucose oxidase 32.
  • the enzyme and its substrate are injected in operation, which allows in particular adjusting the intensity of the catalysis of the cathodic reaction, thus the operation of the battery, by modulating the amount of glucose injected.
  • the catalysis of the anodic reaction is provided by platinum.
  • outlets 34 are provided to ensure the renewal of the oxidant and fuel, enzymes and substrates.
  • the arrival 32 of glucose and glucose oxidase is used to inject 1 ml of a solution containing 20 mM glucose and the glucose oxidase content indicated in Table 2, at the beginning of operation of the battery. .
  • ⁇ / u> Glucose oxidase concentration 0 unit / L 1 unit / L 10 units / L 100 units / L Report (Power with enzyme / power without enzyme) 1 1.15 1.15 1.28

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Catalysts (AREA)
  • Enzymes And Modification Thereof (AREA)

Claims (14)

  1. Brennstoffzelle mit Protonenaustauschmembran, die umfasst:
    - ein Kathodenabteil, das eine Kathode, ein Oxidationsmittel, bestehend aus Sauerstoff, und mindestens einen enzymatischen Katalysator umfasst;
    - ein Anodenabteil, das eine Anode, einen Brennstoff und mindestens einen Katalysator umfasst,
    wobei die genannten Anoden- und Kathoden-Abteile beiderseits der genannten Membran angeordnet sind,
    und die Brennstoffzelle dadurch gekennzeichnet ist, dass
    der genannte enzymatische Katalysator des Kathodenabteils ein Enzym vom Oxydoreduktase-Typ ist, das in der Lage ist, die Oxidation eines geeigneten Substrats und die Reduktion von Sauerstoff zu Wasserstoffperoxid zu katalysieren, wobei das genannte Wasserstoffperoxid die Aufgabe erfüllt, die aus der Kathode stammenden Elektronen direkt aufzunehmen.
  2. Brennstoffzelle nach Anspruch 1, dadurch gekennzeichnet, dass das Enzym vom Oxydoreduktase-Typ außerdem geeignet ist, durch Umsetzung mit dem genannten geeigneten Substrat eine Ansäuerung des Kathodenabteils herbeizuführen.
  3. Brennstoffzelle nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Enzym vom Oxydoreduktase-Typ des Kathodenabteils ausgewählt ist aus der Gruppe, die besteht aus Galactose-Oxidase, Glucose-Oxidase, Pyruvat-Oxidase, Glutamat-Oxidase und Alkohol-Oxidasen.
  4. Brennstoffzelle nach Anspruch 3, dadurch gekennzeichnet, dass das Enzym vom Oxidoreduktase-Typ Glucose-Oxidase ist.
  5. Brennstoffzelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Kathode aus einem Material besteht, das ausgewählt ist aus der Gruppe, die besteht aus nicht rostenden Stählen, Aluminium-, Nickel- oder Titan-Legierungen und elektrisch leitenden Polymeren.
  6. Brennstoffzelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Katalysator des Anodenabteils ein Enzym ist, das in der Lage ist, die Oxidation eines geeigneten Substrats zu katalysieren, wobei das genannte Substrat die Funktion eines Brennstoffs erfüllt.
  7. Brennstoffzelle nach Anspruch 6, dadurch gekennzeichnet, dass das Enzym des Anodenabteils außerdem geeignet ist, durch Umsetzung mit dem genannten geeigneten Substrat eine Ansäuerung des Anodenabteils zu bewirken.
  8. Brennstoffzelle nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass das Enzym des Anodenabteils ausgewählt ist aus der Gruppe, die besteht aus Hydrogenasen, Glucose-Oxidase, Galactose-Oxidase und Alkohol-Oxidasen.
  9. Brennstoffzelle nach Anspruch 8, dadurch gekennzeichnet, dass das Enzym des Anodenabteils Glucose-Oxidase ist und der Brennstoff Glucose ist.
  10. Brennstoffzelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es sich dabei um eine Brennstoffzelle mit Gasdiffusion handelt,
  11. Brennstoffzelle nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass es sich dabei um eine Brennstoffzelle handelt, die in wässrigem Medium funktioniert.
  12. Brennstoffzelle nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass das Enzym oder die Enzyme des Anoden- und/oder Kathodenabteils und das Substrat oder die Substrate kontinuierlich oder diskontinuierlich in ihre jeweiligen Abteile während der Funktion der Brennstoffzelle eingeführt werden.
  13. Brennstoffzelle nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass das Enzym oder die Enzyme des Anoden- und/oder Kathodenabteils an der Anode und/oder der Kathode adsorbiert sind.
  14. Brennstoffzelle nach Anspruch 11, dadurch gekennzeichnet, dass das Enzym oder die Enzyme direkt in das wässrige Medium der Anoden- und/oder Kathodenabteile beim Zusammenbau der Brennstoffzelle eingeführt wird (werden).
EP03717375A 2002-02-07 2003-02-05 Brennstoffzelle mit oxidoreduktase-enzymen im kathoderaum oder ggf. anodenraum Expired - Lifetime EP1497885B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0201488A FR2835655B1 (fr) 2002-02-07 2002-02-07 Pile a combustible, utilisant des enzymes en tant que catalyseurs des reactions cathodique et/ou anodique
FR0201488 2002-02-07
PCT/FR2003/000354 WO2003067697A2 (fr) 2002-02-07 2003-02-05 Pile a combustible, utilisant dans le compartiment cathodique et eventuellement dans le compartiment anodique des enzymes de type oxydoreductase

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EP1497885A2 EP1497885A2 (de) 2005-01-19
EP1497885B1 true EP1497885B1 (de) 2006-11-22

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EP03717375A Expired - Lifetime EP1497885B1 (de) 2002-02-07 2003-02-05 Brennstoffzelle mit oxidoreduktase-enzymen im kathoderaum oder ggf. anodenraum

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US (2) US7655345B2 (de)
EP (1) EP1497885B1 (de)
AT (1) ATE346391T1 (de)
AU (1) AU2003222359A1 (de)
CA (1) CA2475062C (de)
DE (1) DE60309854T2 (de)
ES (1) ES2277637T3 (de)
FR (1) FR2835655B1 (de)
WO (1) WO2003067697A2 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7638228B2 (en) 2002-11-27 2009-12-29 Saint Louis University Enzyme immobilization for use in biofuel cells and sensors
US7709134B2 (en) * 2004-03-15 2010-05-04 St. Louis University Microfluidic biofuel cell
WO2006132595A1 (en) * 2005-06-04 2006-12-14 Agency For Science, Technology And Research Laminated battery
WO2007084249A2 (en) 2005-11-02 2007-07-26 St.Louis University Direct electron transfer using enzymes in bioanodes, biocathodes, and biofuel cells
US8404396B2 (en) 2007-05-14 2013-03-26 Brigham Young University Fuel cell and method for generating electric power
FR2930076B1 (fr) 2008-04-09 2011-06-03 Univ Joseph Fourier Biopile a rendement ameliore

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5769668A (en) * 1980-10-16 1982-04-28 Matsushita Electric Ind Co Ltd Enzyme electrode
US5624537A (en) * 1994-09-20 1997-04-29 The University Of British Columbia - University-Industry Liaison Office Biosensor and interface membrane
US6294281B1 (en) * 1998-06-17 2001-09-25 Therasense, Inc. Biological fuel cell and method
US6500571B2 (en) * 1998-08-19 2002-12-31 Powerzyme, Inc. Enzymatic fuel cell

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Publication number Publication date
US20050164073A1 (en) 2005-07-28
DE60309854D1 (de) 2007-01-04
ATE346391T1 (de) 2006-12-15
CA2475062A1 (en) 2003-08-14
WO2003067697A2 (fr) 2003-08-14
DE60309854T2 (de) 2007-12-13
US20100112414A1 (en) 2010-05-06
FR2835655B1 (fr) 2004-03-12
AU2003222359A1 (en) 2003-09-02
US7655345B2 (en) 2010-02-02
WO2003067697A3 (fr) 2004-11-04
EP1497885A2 (de) 2005-01-19
FR2835655A1 (fr) 2003-08-08
CA2475062C (en) 2011-11-08
US7875394B2 (en) 2011-01-25
ES2277637T3 (es) 2007-07-16

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